Synthetic rubber composition containing a reaction product of sulfur dichloride, an aldehyde and an alkyl phenol



Patented .luly 2i}, 1%48 rre sreres orrlou SYNTHETIC RUBBER comroslrtoN cork- VAILABLE COPY TAKNING A REACTION PRODUCT OF SUL- FUR BIEHLORIDE, AN ALDEHYDE AND [KN ALKYL PHENOL 18 Claims. .1

This Invention related to improved synthetic: rubber compositions and methods of using the same. More particularly, it relates to resins prepared from sulfur dichloride, a substituted phenol, and an aldehyde, and to the use of such resins to impart tack to uncured, rubber-like copolymers of a conjugated dlcne-for example. cutedlcnc, iscprcne, 2-oyanobutadlcne, cyclopentaclleue, methylpentadlenc, plpcrylcnc, dlmethylbutadlcne, etaend a. vinyl aromatic compound--for example, styrene, clphwmetnyl styrene, nuclcor-substltuted styrencs, monochlorostyrene, dlcl'llovostyrenc, vinylnaphthalene, vlnylbiphcnyl. vlnylczwhazolc, Z-vlnyl-S-ethylpyridine, 2-etllyl-fi--Vlnylpyrldlne, etc. The tacltlficr may advantageously be employed wlth a rubber-like copolymer formed in the presence of rosin soap, or other teckltylng material added In other ways. The invention will be described more particularly as it relates to the rubber-like ell-polymer of hutodlcnc and styrene known :15 GIL-S.

Difficulty hos, been ellperlcnecd in the mechanlea} processine of Gilt/5 because lt does not noturaliy have c." tool; Bhlit .lultural rubber posrzessaa. For example, Wlum natural rubber ls used in building a tire, the venous plies of fabric treated with the uncured rubber readily adhere to one another when touched together or pressed together by hand Furthermore, the tread stock which contains no fabric is sufficiently tacky so that it retains its place when merely pressed into posltlon. The various parts of a tire prcpared with uncured natural rubber, when assembled, adhere to one another so that the green tire produced by pressing together the uncured parts will withstand rather rough handling without damage.

The use ol in tires has necesslteted a. change in the lmudllng procedure because the rubber-llke copolymers of butadlene and styrene GR-S) are not tacky. Rough handling muses the plies to separate, and separations and fell ures 1n the cured tire may result from lack ol tack tn the GR-S stock used in bulldlng the tire.

According to the present invention, tuck ls lmparted to rubber-like copolymcrs of butacllcne and styrene, etc, by the incorporation thereln of a resln from a hydrocaroomsubstltuted phenol, an aldehyde, and sulfur dichloride. Such teoklfiers lncorporatcd in the uncured amok glve tack without adversely affecting the properties of the cured rubber obtained therefrom, and the decree of tack elven the (JR--55, etc, may approach that of natural rubber. The tacklflcr may be incorpomted into GI LS stocks used for coatlng fabric, forming tlre treads, ale, to import sufllclent tech to these tire component parts to permlt them to be used In building tires in the some manner as one-half hours following this addition.

it was previously employed with natural rubber stocks.

Various experiments have been made with the use of thls type of tuclclller in uncured, rubberlllce copolymcrs of a conjugated dlcne and a vinyl oromctlc compound. In recording the results of the experiments in the following tables, the tech of copolymers whlch are completely locking in. tucklncss ls rated as l), and the tacklness of milled, uncured natural rubber is rated as 10. Two sheets havlnlg' such high tacklncss of 10, when pressed together, have sufilclcnt adhercnce that tears may occur when an effort is made to separate them. The closer the tack number approaches 16, the better the took.

The tucklllers may be produced by first reactlng the aldehyde and phenol and then treating the product with sulfur dichloride, or my first reuctlng the phenol with sulfur dlchlorldc and then obtaining an eldchycle reaction product therefrom. The following examples are illustratlve:

EXAMPLE 1 Seventy--llyc grulm of pum-tertiary-outgrpheuol were added to 37.5 grams of 48 per cent formalin LRQUIE'OUS formaldehyde). Forty grams of e 10 per cent solution of sodium hydroxide were then added end the mixture stirred or 15 home at 25 C. The .lxture was zleutrallzed with acetic acid and tell: u up in ethylene dichlorlde. The bulk of the at 2.1521 was removed by decantutlon, and the remainder was dlstllled off with home of the solvent until a clear distillate was observed. The dried product was diluted with etl'lylcnc dichloride until u solutlon was obtained that contained approximately 29 per cent of the phenolJormcldehydc reaction product. There was added to the; solution at the reflux temperature of the solvent 28.4 grams of sulfur dichloride dissolved in on equal volume of ethylcnc dichloride. The addition of the sulfur d!- chlorldc was made over a. one-helf-hour period, and the refluxing was continued for one and The solvent was removed on a steam distillation loath under reduced PILZSNJL'U. The product ls a dark brown resin with a softening point of 63-83 C. The yield was 86.9 alums.

Emmett". 2

Sevcnty-llve grams of para-tcrtlary-butylphenol cllssolved in 300 grams of ethylene (llchloride were treated at the reflux temperature wlth 20.6 grams of sulfur dlchlorldc dissolved in 20.8 grams cl ethylene dichloride. The addltlon was mode over at one-hour period, and the re- Iluxlng was continued for one-hall hour thereafter. The solution was then cooled and washed with water until neutral to litmus. The ethylene ammo? 3 dichloride solution oi this phenol sulfide was returned to the reaction flask along with 42 grams 01' 40 per cent formaldehyde and 40 grams of 10 per cent sodium hydroxide solution. This mixture was stirred vigorously at 25 C. tor one hour and then at 70 C, tor three more hours. The mass was cooled and the water layer discarded. The solution was then heated under reduced pressure and the solvent removed up to a temperature of 100 C. The product, a hard, yellow resin which fused in the flask. was dug out. It has a softening and decomposition point oi approximately Mil-2S0 C. The yield was 81.5 grams.

Exam: 3

Seventy-five grams of para-tertlary-butylphenol, 43 grams of 35 per cent formalin, and 40 grams of 20 per cent sodium hydroxide were heated under reflux with stirring at 85-95 C. for three and 9. half hours. The viscous syrup was poured into cracked ice in a mortar and pulverized. The mass was neutralized with 8 milliliters glacial acetic acid, washed several times with ice water, and filtered. Weight 140 grams.

The resin was placed in a flask and dissolved in 600 grams of ethylene dichloride by gently warming. Forty grains of water were removed by decantation, and a small amount or the solvent was distilled to remove the last traces of water.

The solvent was replaced, and to the stirred mixture at the reflux temperature was added a 50 per cent ethylene dichloride solution oi sulfur dichloride containing 46.4 grams of the latter. The addition was made over a one-hali-hour period. Rcfluxing was continued for one and a half hours. The solvent was removed on the steam bath under vacuum. The result was 110 grams of a clear brown resin which softened hetwecn 80-110 C.

Erma: 4

One hundred grams of a para-tertiary-butyiphenol-acctaldehyde resin (softening point '75- 78 C.) were dissolved in 400 grams of ethylene dichloride, and to this refluxing solution there were added. over a 45-minute period, 6.0 grams of sulfur dichloride dissolved in an equal weight of ethylene dichloride. Refiuxing was continued for one and one-half hours, and the solvent was removed on the steam bath under reduced pressure. The resin is amber to brown in color and has a softening range from 85-i00 C.

Emma: 5

Para-tertiary-decylphenol (46.8 grams), 15.0 grams or 40 per cent formaldehyde, and 20.0 grams oi per cent sodium hydroxide were stirred for 17 hours at 25 C. The reaction mixture was neutralized with acetic acid. The doc-- ylph'enol-Iormaldehyde product was dissolved in 250 grams of ethylene dichloride and distilled until dry. The solvent was replaced, and 17.9 grams of sulfur dichloride dissolved in 20 grams of ethylen dichloride were added over a onehali-hour period at the reflux temperature oi the mixture. Rlefluxing was continued for one hour, and the solvent was then removed on the steam bath under reduced pressure. The product is a dark brown, soft resin which softens between 60 and 80 0.

EXAMPLE 6 Eighty-two grams of ortho-tertiary-amylpheml were added to 37.5 grams of 40 per cent formalin. Forty grams of a 10 per cent aqueous solution of sodium hydroxide were then added. and the mixture was stirred at room temperature for 18 hours. The reaction mixture was neutralized with acetic acid. The product was taken up in ethylene dichloride and dried by dccantatlon and the distillation of a small amount of the solvent.

A solution 01' such amylphenol-formaldehyde reaction product was adjusted to contain 53 grams of reaction product in 215 grams oi ethylone dichlor de. To this refluxing solution there was dropped, during the course of 30 minutes, a. 50 per cent solution oi 25.9 grams of sulfur dichloride in ethylene dichloride. The refluxing was continued for 2 hours to remove hydrogen chloride from the mixture. and then the solvent was distilled on a steam bath and under reduced pressure. The product is a soft. dark resin with a softening point of 60'80 C. The yield was quantitative.

Exauru: '7

Seventy-five grams or para-tertiary-hutylpheno], 96 grams of glyoxai (ethandial), and 5 grams of concentrated sulfuric acid were stirred at 66 C. for one-half hour. Then the temperature was raised to -90" C., and stirring was continued for two more hours. The mass was neutralized with 50 milliliters of 10 per cent sodium hydroxide, extracted with 400 grams oi ethylene dichloride and the water removed by decantation and distillation of a small portion oi the solvent. The sol vent was replaced, and 40 grams of sulfur dichloride dissolved in an equal weight of ethylene di' chloride were added at the reflux temperature of the mixture. The addition 01' sulfur dichloiide was made over a two-hour period with stirring, and the mixture was refluxed one hour following the addition. The solvent was removed on the steam both under reduced pressure. The resin is brown in color, having a softening range from 85 to 85 C.

Other tackiilers may be similarly produced by treating other phenols substituted in the ortho or para position with a hydrocarbon radical containing about three to about ten carbon atoms. Other processes of forming the products may be utilized. The phenols which are preferred are those substituted in the para position with an alkyl radical containing four to seven carbon BLOIliS, especially the secondary and tertiary para-butyland amylphenols. Other phenols which may be employed include, for example:

p-cyclohexylphenol p-tertiary-butyl-m-cresol p-hcxylphenol p-hcptylphenol p-n-alnylphenol p-secondary-butyl-mcresol p-n-butylphenol p-neopentylphenol p-plienylphenol p isoamylphenol p-il,1,3,3-tetramethylbutyl) phenol p-isopropylphenol o-amylphenol o-butylphenol o- (2-hcpty1) phenol o-cyclohexyiphenol o-phenylphenol The aldehyde-s which may be employed include formaldehyde, acetaldehydc, and glyoxal.

Experiments showed that improved tack was obtained when the uncured copolymer was compounded with a softener, such as a coal-tar oil. pine tar, dipentene, etc. The addition of a compound such as zinc resinate (or zinc rosinate) improved the tack. The tackifier may he added to the latex or may be compounded on a mill or in an internal mixer. It is necessary to obtain a certain amount of solution into the copolymer, but any means of accomplishing this-whether or not associated with other compounding ingredients and whether or not heat is applied-is satisfactory.

The first table gives the tack rating of a copolymcr (GR-S) obtained from 75 parts of hutadiene and 25 parts of styrene with parts of each of the two resins prepared according to Examples 1 1 and 2 per 100 parts of GR-S:

TABLE I Tackiiler: Tack rating None U p-Tcrtiory hutylphenoi-formaldehydesulfur dichloride reaction product (Exride-formaldehyde reaction product (Example 2) 6 A copoiymer of butadiene and styrene obtained in an emulsion containing rosin soap was compounded according to the following formula:

Formula 1 Parts Copolymer 50.00 Tacitifier 2.50 Pine tar 1.25 Dipentene 1.50

The tackiiicrs of Examples 1 and 2 were componnded in this formula. The products were tested with the following results:

TABLE II Tacin'fler: Tack rating None (but containing pine tar and di- Softeners improve the tack, particularly in the case of high-melting tackifiers, by aiding the so lution of the tackifier in the copolymer.

The following table records the results obtained by adding to 100 parts of GR-S 10 parts of tilt tackifler of Example 4:

TnBLE III Taclcifier: Tack rating None -4--- 0 p-Tertiary-butylphenoi acetaldehydesulfur dichloride reaction product 6-! The tackifier of Example 3 was compounded according to different formulae and then tested for tack. The formula are given below:

Formula 2 Parts GR-S s. 50.0 Tackificr 2.5 Dipentene 2.5

Formula 3 Parts GR-S 50.0 Tackifler 2.5 Dlpentene 2.5 Easy-processing channel black 15.6

It is recognized that channel black reduces tack, and the results oi" the experiment are recorded to show that even in the presence of this much black, the compound still had good tack. The results of the tests are recorded in the following table:

TABLE IV GR-S composition: Tack rating Formula 2 -e 9 Formula 2 control (no tackifier) e- 1 Formula 3 8 Formula 3 control (no tackifier) (J-1 The tackiiiers oi Examples 5 6, and T were tested by mixing 10 parts with parts of (33-8. The results are given in the following table:

TABLE V Tackifier: Tack rating None (l p lertiary-decylphenoi formaldehydesulfur dichloride reaction product (Example 5) 4 o-Tertiary-a1nylphenol formaldehydesulfur dichloride reaction product (Example 6) 5 p--Tertiory-butylphenoi glyoxahsulfur dichloride reaction product (Exam- GR-S latex cements Htqucous dispersions) and ordinary solvent cements of GR-S type synthetic rubbers are notoriously poor in adhesive properties. However. when such cements contain a taclrifier in accordance with the present inven tion, the cements exhibit substantially improved powers of adhesion, approaching conventional natural rubber cements in this respect.

The invention is not limited to the formulae disclosed or to other detail of th disclosure. Modifications may be made without departing from the scope oi the appended claims.

What I claim is:

1. Tacky, uncured, rubber-like composition composed of copolymer of a conjugated diene and a vinyl aromatic compound which includes as a tacklfler a reaction product of (1) sulfur dichloride. (2) an aldehyde of the class consisting of formaldehyde, acctaldchyde, and giyoxal. and (3) a phenol oi the class which consists of phenols substituted in the ortho position by a hydrocarhon radical containing three to ten carbon atoms and phenols substituted in the para position by a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being acidcatalyzed.

2. Tacky. uncured, rubber-like composition composed essentially of butadicne-styrene copolymcr which includes as a tackifler a reaction product of (I) sulfur dichloride, (2) an aldehyde of the class consisting of formaldehyde acetalda hyde, and ulyoxal. and 3) a phenol of the class which consists of phenols substituted in the ortho position by a hydrocarbon radical containing three to ten carbon atoms and phenols substi tutcd in the para position by a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being acid-catalyzed.

3. A tacky composition which contains rubberlike copolymer of butadiene and styrene and a tackiflcr which is the sulfur dichloride reaction product or a product obtained by the reaction of an aldehyde of the class consisting of formaldehyde. acetaldehyde, and glyoxal and an alkylphenol having para to the hydroxyl group an alltyl group containing four to seven carbon atoms, the aldehyde reaction being acid-catalyzed.

4. A tacky composition which contains uncured. rubber-like copolymer of butadiene and styrene and as a tackifier the product of the acid-catalyzed reaction of formaldehyde and the reaction product of sulfur dichloride and an al kylphenol which contains in the position para to the hydroxyl group an alkyl group containing four to seven carbon atoms.

5. A tacky composition which contains uncured. rubber-like copolymcr of butadlene and styrene and as a tackifier the sulfur dichloride reaction product of the acid-catalyzed reaction product of formaldehyde and para-branched chain-butylphenoi.

6. A tacky composition which contains uncured, rubber-like copolymor or butadlene and styrene and the acid-catalyzed formaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-ehain-butylphenol.

'l. A tacky composition which contains uncured, rubber-like copolymer oi butadiene and styrene and the ncidmatalyzed formaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-chain amylphenol.

8. A tacky composition which contains uncured. rubber-lil e copolymer of butadiene and styrene and as a tackifler the sulfur dichloride reaction product 01 the acid-catalyzed reaction product of an aldehyde oi the class consisting of formaldehyde. acctalclehyde, and glyoxal and a phenol oi the class consisting of ortho-alkylphcnols and ara-alkylphenois, the allryl groups being branched chain and containing no more than ten carbon atoms.

9. A tacky composition which COXitillIlS uncured, rubber-like copoiymer of butadiene and styrene and acidcatalyaed the acetaldehyde reaction product of the reaction product of sulfur dichloride and para-branched-chain-amylphenol.

10. The process oi imparting tacit to a rubberlilse copolymer of a conjugated dicnc and a vinyl aromatic compound which comprises incorporating in the copolymcr the reaction product of 1) sulfur dichloride, 42) an aldehyde of the class consisting of formaldehyde, acctnldehycle, and glyoxai, and 3 2. phenol of the class which con sists of phenols substituted in the ortho position by a hydrocarbon radical containing three to ten carbon atoms and phenols substituted in the para position by a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being acid-catalyzed.

11. The process of imparting tack to parts formed of rubber-like butadlene-styrene copolymer and producing an article therefrom which comprises incorporating in the copolymer from which the parts are made sufficient tackiilcr to cause the parts to coherc when brought in contact. forming the green arlicie from the parts. and then vulcanizlng; the tackiller being the reactlon product or an aldehyde of the class con sistlng of formaldehyde, acetaldchyde, and glyoxai, on the reaction product of sulfur dichloride and a phenol oi the class which consists of phenois substituted in the ortho position by a hydrocarbon radical containing three to ten carbon atoms and phenols substituted in the para position by a hydrocarbon radical containing three to ten carbon atoms, the aldehyde reaction being acid-catalyzed.

12. The process of imparting took to parts formed of rubber-like butadiene-styxene copolymer and producing an article therefrom which comprises incorporating in the copolymer from which the parts are made suiiicient tackifier to cause the parts to cohere when brought in contact. forming the green article from the parts. and then vulcaniring; the tackitler being the ulfur-dichloride reaction product of the acid-catalyzed reaction product of an aldehyde of the ciass consisting of formaldehyde, acetaldchyde, and glyoxal and a phenol of the class which consiits of phenols uliistitutcd in the ortho position by a hydrocarbon radical containimz, three to ten carbon atoms and phenols substituted in the para position by a hydrocarbon radical containing three to ten carbon atoms.

13. A tacky composition which contains rubbery copolymer of butadiene and styrene and a tackliler which is the sulfur dichloride reaction product of a product obtained by the reaction with acid catalyst of on alicylphenol having para to the hydroxyl group an alltyl group containing four to seven carbon atoms and an aldehyde of the group consisting of formaldehyde, acetaldchydc and glyoxai.

14, A tacky composition which contain rubbery copolymcr 0i butadicne and styrene and a tackliier which is the sulfur dichloride reaction product of a product obtained by the reaction with acid catalyst of formaldehyde and an allcyl phenol having porn to the hydronyi group an di icyl group containing tour to seven car ort atoms.

15. A tacky composition which contains rubbery copulymcr of butadiene and styrene and a tackiiier which is the sulfur dichloride reaction product of a product obtained by the reaction with acid catalyst of uciituldcliyde and an alkylphenol having para to the hydroxyi group an alkyl group containing our to seven carbon atoms.

16. A tacky composition which contains uncured rubbery copolymer oi hutudiene and styrene and as a tackiiicr the ulfur dichloride reaction product of the reaction product with acid catalyst oi para-branched-chain-butyl phenol and an aldehyde of the class consisting of formaldehyde. acetaldchyde and glyoxal.

1'1. A tacky composition which contains uncured rubbery copol mer of butadiene and styrene and as a tackiiier the suliur dichloride reaction product of the reaction with acid catalyst of parahranci1cd-cliain-aii1y1 phenol and an aldehyde oi the class consisting oi formaldehyde, acetaidchyde and glyoxal.

18. The process of imparting tack to parts formed oi. rubbery butadicnc-styrenc copolymcr and producing an article therefrom which comprises incorporating in the copolymer from which the parts are made sui'ilcient tackifier to cause the parts to cohcre when brought into contact, termin -r the croen article from the parts. and then vulcanlzinc; the taekifier being the sulfur dichlo ide reaction product oi the reaction product with acid catalyst of an aldehyde of the class conslstlnc of formaldehyde, acetaldchydo and glyoxal and a plicnul of the class which consists of phenols having in the ortho position a hydrocarbon substiluent containing three to ten cal- REFERENCES (JITED The following referenws are of record in the file of this patent:

UNITED STATES PATENTS Home Data Samuel Mar. 5, 19229 Number Number Number Patent No. 2,445,735.

HARRY E. ALB JET It is herebv certified that; error appears in the printed. spocifioation of the above numbered put/ ent rwtguiring roz'rootion as follows:

iii?

Name Date Eilis M Jan. 6, 1931 Mikeslm Dec. 6, 1938 Roseu June 17, 1941 lbllllkl. W .M... Jan. 27, 1942 FOREIGN PATENTS Country Date Ital Oct, 30, 1939 Ciommny July 14, 1939 July 20, 1948.

Column 7, lino 48, claim 9, for aoidwntalyzed the road tfae aczkflmoiaigmed;

and hm the said Letters Patent 311011151 bk! rum] with this cprrficbion therein. that the some may conform. to the record of the moo 1n the Pmont; Ufhoe.

Signed and unwind this 7th day of December, A, D. 12MB,

REFERENCES (JITED The following referenws are of record in the file of this patent:

UNITED STATES PATENTS Home Data Samuel Mar. 5, 19229 Number Number Number Patent No. 2,445,735.

HARRY E. ALB JET It is herebv certified that; error appears in the printed. spocifioation of the above numbered put/ ent rwtguiring roz'rootion as follows:

iii?

Name Date Eilis M Jan. 6, 1931 Mikeslm Dec. 6, 1938 Roseu June 17, 1941 lbllllkl. W .M... Jan. 27, 1942 FOREIGN PATENTS Country Date Ital Oct, 30, 1939 Ciommny July 14, 1939 July 20, 1948.

Column 7, lino 48, claim 9, for aoidwntalyzed the road tfae aczkflmoiaigmed;

and hm the said Letters Patent 311011151 bk! rum] with this cprrficbion therein. that the some may conform. to the record of the moo 1n the Pmont; Ufhoe.

Signed and unwind this 7th day of December, A, D. 12MB, 

